Gel electrophoresis coupled to inductively coupled plasma-mass spectrometry using species-specific isotope dilution for iodide and iodate determination in aerosols

In this paper, we present an online coupling of gel electrophoresis (GE) and inductively coupled plasma-mass spectrometry (ICP-MS) for the determination of iodine species (iodide and iodate) in liquid (seawater) and aerosol samples. For the first time, this approach is applied to the analysis of small molecules, and initial systematic investigations revealed that the migration behavior as well as the detection sensitivity strongly depends on the matrix (e.g., high concentrations of chloride). These effects could consequently affect the accuracy of analytical results, so that they need to be considered for the analysis of real samples. The technique used for quantification is species-specific isotope dilution analysis (ssIDA), which is a matrix-independent calibration method under certain conditions. We demonstrate that the use of 129I-enriched iodide and iodate allows the correction of the impact of the matrix on both, the electrophoretic migration and the detection sensitivity of the ICP-MS. After optimization, this coupling offers a novel and alternative method in the analysis of iodine compounds in various matrices. Here, we demonstrate the analytical capability of the technique for the chemical characterization of marine aerosols. The results show the presence of iodide and iodate at the ng m(-3) and sub-ng m(-3) level in the investigated aerosol samples, which were taken at the coastal research station in Mace Head, Ireland. These results are in good agreement with other recent studies, which demonstrated that the iodine chemistry in the marine atmosphere is only poorly understood. In addition to iodide and iodate, another iodine compound could be separated and detected in certain samples with high total iodine concentrations and was identified as elemental iodine, probably in form of triiodide, by peak matching. However, it may arise from an artifact during sample preparation.     

Determination of iodine in oyster tissue by isotope dilution laser resonance ionization mass spectrometry

The technique of laser resonance ionization mass spectrometry has been combined with isotope dilution analysis to determine iodine in oyster tissue. The long-lived radioisotope, 129I, was used to spike the samples. Samples were equilibrated with the 129I, wet ashed under controlled conditions, and iodine separated by coprecipitation with silver chloride. The analyte was dried as silver ammonium iodide upon a tantalum filament from which iodine was thermally desorbed in the resonance ionization mass spectrometry instrument. A single-color, two-photon resonant plus one-photon ionization scheme was used to form positive iodine ions. Long-lived iodine signals were achieved from 100 ng of iodine. The precision of 127I/129I measurement has been evaluated by replicate determinations of the spike, the spike calibration samples, and the oyster tissue samples and was 1.0%. Measurement precision among samples was 1.9% for the spike calibration and 1.4% for the oyster tissue. The concentration of iodine determined in SRM 1566a, Oyster Tissue, was 4.44 micrograms/g with an estimate of the overall uncertainty for the analysis of +/- 0.12 microgram/g.     

Isotope dilution gas chromatography/mass spectrometry for the determination of nickel in biological materials

Precise and accurate methods are required to measure nickel in urine and serum samples to identify clinical states of either deficiency or toxicity. This paper presents an isotope dilution gas chromatography/mass spectrometry method for the measurement of nickel in biological samples. The method involves the preparation of a thermally stable and volatile nickel chelate using lithium bis(trifluoroethyl)dithiocarbamate as the chelating agent. Conditions were optimized for the digestion of the sample and quantitative preparation of chelate as well as the precise and accurate measurements of the isotope ratios using a capillary column gas chromatograph with a general purpose mass spectrometer. The memory effect between samples of different isotope ratios was evaluated and was found to be negligible. The quantitative accuracy of isotope dilution was validated by measuring nickel in the NIST freeze-dried urine reference material, SRM 2670, with comparison to the recommended value.     

Microwave acid digestion and preconcentration neutron activation analysis of biological and diet samples for iodine

A simple preconcentration neutron activation analysis (PNAA) method has been developed for the determination of low levels of iodine in biological and nutritional materials. The method involves dissolution of the samples by microwave digestion in the presence of acids in closed Teflon bombs and preconcentration of total iodine, after reduction to iodide with hydrazine sulfate, by coprecipitation with bismuth sulfide. The effects of different factors such as acidity, time for complete precipitation, and concentrations of bismuth, sulfide, and diverse ions on the quantitative recovery of iodide have been studied. The absolute detection limit of the PNAA method is 5 ng of iodine. Precision of measurement, expressed in terms of relative standard deviation, is about 5% at 100 ppb and 10% at 20 ppb levels of iodine. The PNAA method has been applied to several biological reference materials and total diet samples.     

Analysis of acrylamide in water using a coevaporation preparative step and isotope dilution liquid chromatography tandem mass spectrometry

Acrylamide is a probable human carcinogen, and the drinking water quality guideline for this compound is 0.5 mg/L. However, analysis of this compound in water is difficult because of its very high water solubility, which limits the efficiency of sample preconcentration prior to analysis. We developed a robust and sensitive analytical method for the determination of trace quantities of acrylamide in samples of water using a novel preparative technique and isotope dilution liquid chromatography tandem mass spectrometry with atmospheric pressure chemical ionization as the ion source (LC-APCI-MS/MS). The preparative method involves coevaporation of acrylamide with water at pH 10 using a rotary evaporator, followed by acidification to pH 3.0 and concentration of the sample prior to analysis by LC-APCI-MS/MS. To compensate for the loss of the analyte during sample preparation and signal suppression due to interference from the sample matrix, isotope dilution with acrylamide-d3 was used for quantitation. Using this method, analyte recoveries ranged from 74 to 103% for acrylamide spiked into water at a concentration of 0.4 ng/mL. The limit of detection and limit of quantification (LOQ) for acrylamide in water were 0.02 and 0.06 ng/mL, respectively. This method was successfully applied to determine trace levels of acrylamide in samples of river water and in runoff from an agricultural field to which municipal biosolids (i.e., sludge) had been applied. Concentrations of acrylamide in these samples ranged from 相似文献   

Direct determination of trace elements in powdered samples by in-cell isotope dilution femtosecond laser ablation ICPMS

A method has been developed for the direct and simultaneous multielement determination of Cu, Zn, Sn, and Pb in soil and sediment samples using femtosecond laser ablation inductively coupled plasma mass spectrometry (fs-LA-ICPMS) in combination with isotope dilution mass spectrometry (IDMS). The in-cell isotope dilution fs-LA-ICPMS method proposed in this work was based on the quasi-simultaneous ablation of the natural abundance sample and the isotopically enriched solid spike, which was performed using a high repetition rate laser and a fast scanning beam device in a combined manner. Both the sample preparation procedure and the total analysis time have been drastically reduced, in comparison with previous approaches, since a unique multielement isotopically enriched solid spike was employed to analyze different powdered samples. Numerous experimental parameters were carefully selected (e.g., carrier gas flow rate, inlet diameter of the ablation cell, sample translation speed, scanner speed, etc.) in order to ensure the complete mixing between the sample and the solid spike aerosols. The proposed in-cell fs-LA-ICP-IDMS method was tested for the analysis of two soil (CRM 142R, GBW-07405) and two sediment (PACS-2, IAEA-405) reference materials, and the analysis of Cu, Zn, Sn, and Pb yielded good agreement of usually not more than 10% deviation from the certified values and precisions of less than 15% relative standard deviation. Furthermore, the concentrations were in agreement not only with the certified values but also with those obtained by ICP-IDMS after the microwave-assisted digestion of the solid samples, demonstrating therefore that in-cell fs-LA-ICP-IDMS opens the possibility for accurate and precise determinations of trace elements in powdered samples reducing the total sample preparation time to less than 5 min. Additionally, scanning electron microscope measurements showed that the aerosol generated by in-cell fs-LA-ICP-IDMS predominantly consisted of linear agglomerates of small particles (in the order of few tens of nanometers) and a few large spherical particles with diameters below 225 nm.     

Towards absolute quantification of therapeutic monoclonal antibody in serum by LC-MS/MS using isotope-labeled antibody standard and protein cleavage isotope dilution mass spectrometry

Although LC-MS methods are increasingly used for the absolute quantification of proteins, the lack of appropriate internal standard (IS) hinders the development of rapid and standardized analytical methods for both in vitro and in vivo studies. Here, we have developed a novel method for the absolute quantification of a therapeutic protein, which is monoclonal antibody (mAb). The method combines liquid chromatography tandem mass spectrometry (LC-MS/MS) and protein cleavage isotope dilution mass spectrometry with the isotope-labeled mAb as IS. The latter was identical to the analyzed mAb with the exception that each threonine contains four (13)C atoms and one (15)N atom. Serum samples were spiked with IS prior to the overnight trypsin digestion and subsequent sample cleanup. Sample extracts were analyzed on a C18 ACE column (150 mm x 4.6 mm) using an LC gradient time of 11 min. Endogenous mAb concentrations were determined by calculating the peak height ratio of its signature peptide to the corresponding isotope-labeled peptide. The linear dynamic range was established between 5.00 and 1000 microg/mL mAb with accuracy and precision within +/-15% at all concentrations and below +/-20% at the LLOQ (lower limit of quantification). The overall method recovery in terms of mAb was 14%. The losses due to sample preparation (digestion and purification) were 72% from which about 32% was due to the first step of the method, the sample digestion. This huge loss during sample preparation strongly emphasizes the necessity to employ an IS right from the beginning. Our method was successfully applied to the mAb quantification in marmoset serum study samples, and the precision obtained on duplicate samples was, in most cases, below 20%. The comparison with enzyme-linked immunosorbent assay (ELISA) showed higher exposure in terms of AUC and Cmax with the LC-MS/MS method. Possible reasons for this discrepancy are discussed in this study. The results of this study indicate that our LC-MS/MS method is a simple, rapid, and precise approach for the therapeutic mAb quantification to support preclinical and clinical studies.     

Simultaneous sample preparation and species-specific isotope dilution mass spectrometry analysis of monomethylmercury and tributyltin in a certified oyster tissue

A rapid, accurate, sensitive, and simple method for simultaneous speciation analysis of mercury and tin in biological samples has been developed. Integrated simultaneous sample preparation for tin and mercury species includes open focused microwave extraction and derivatization via ethylation. Capillary gas chromatography-inductively plasma mass spectrometry (CGC-ICPMS) conditions and parameters affecting the analytical performance were carefully optimized both for species-specific isotope dilution analysis of MMHg and TBT and for conventional analysis of MBT and DBT201Hg-enriched monomethylmercury and 117Sn-enriched tributyltin were used for species-specific isotope dilution mass spectrometry (SIDMS) analysis. As important, accurate isotope dilution analysis requires equilibration between the spike and the analyte to achieve successful analytical procedures. Since the spike stabilization and solubilization are the most critical and time-consuming steps in isotope dilution analysis, different spiking procedures were tested. Simultaneous microwave-assisted spike stabilization and solubilization can be achieved within less than 5 min. This study originally introduces a method for the simultaneous speciation and isotope dilution of mercury and tin in biological tissues. The sample throughput of the procedure was drastically reduced by fastening sample preparation and GC separation steps. The accuracy of the method was tested by both external calibration analysis and species-specific isotope dilution analysis using the first biological reference material certified for multielemental speciation (oyster tissue, CRM 710, IRMM). The results obtained demonstrate that isotope dilution analysis is a powerful method allowing the simultaneous speciation of TBT and MMHg with high precision and excellent accuracy. Analytical problems related to low recovery during sample preparation are thus minimized by SIDMS. In addition, a rapid procedure allows us to establish a performant routine method using CGC-ICPMS technique.     

Accurate determination of human serum transferrin isoforms: Exploring metal-specific isotope dilution analysis as a quantitative proteomic tool

Carbohydrate-deficient transferrin (CDT) measurements are considered a reliable marker for chronic alcohol consumption, and its use is becoming extensive in forensic medicine. However, CDT is not a single molecular entity but refers to a group of sialic acid-deficient transferrin isoforms from mono- to trisialotransferrin. Thus, the development of methods to analyze accurately and precisely individual transferrin isoforms in biological fluids such as serum is of increasing importance. The present work illustrates the use of ICPMS isotope dilution analysis for the quantification of transferrin isoforms once saturated with iron and separated by anion exchange chromatography (Mono Q 5/50) using a mobile phase consisting of a gradient of ammonium acetate (0-250 mM) in 25 mM Tris-acetic acid (pH 6.5). Species-specific and species-unspecific spikes have been explored. In the first part of the study, the use of postcolumn addition of a solution of 200 ng mL(-1) isotopically enriched iron (57Fe, 95%) in 25 mM sodium citrate/citric acid (pH 4) permitted the quantification of individual sialoforms of transferrin (from S2 to S5) in human serum samples of healthy individuals as well as alcoholic patients. Second, the species-specific spike method was performed by synthesizing an isotopically enriched standard of saturated transferrin (saturated with 57Fe). The characterization of the spike was performed by postcolumn reverse isotope dilution analysis (this is, by postcolumn addition of a solution of 200 ng mL(-1) natural iron in sodium citrate/citric acid of pH 4). Also, the stability of the transferrin spike was tested during one week with negligible species transformation. Finally, the enriched transferrin was used to quantify the individual isoforms in the same serum samples obtaining results comparative to those of postcolumn isotope dilution and to those previously published in the literature, demonstrating the suitability of both strategies for quantitative transferrin isoform determination in real samples.     

Automated On-Line Isotope Dilution Analysis with ICP-MS Using Sandwich Flow Injection

An automated flow injection (FI) manifold is described to perform the addition of isotopic spikes to aqueous samples on-line with ICP-MS for isotope dilution (ID) analysis. The manifold uses the sandwich technique (with the nested loop approach) to perform an injection of the isotopic spike solution within a sample (or standard) plug, the resulting sample-spike-sample sequence being pushed toward the nebulizer by a 1% HNO(3) carrier. A standard, which must contain one element not present in the spike solution to allow the determination of the dispersion coefficient, must also be used to allow a reverse isotope dilution analysis, as well as corrections for mass discrimination and/or spectroscopic interferences. Indeed, because the signals from the individual isotopes are monitored continuously, only one isotope free of spectroscopic interference is required for elements whose isotopic distribution does not vary in nature (two isotopes are still needed for the other elements), as a correction for the interference can be made by comparison with the signals from the standard. Furthermore, this automated approach makes ID-ICP-MS a faster method and does not require any preliminary analysis of the sample because the concentration profile resulting from FI allows the selection of the best isotopic ratio. It was successfully applied to the determination of Mo in saline water.     

Species-specific GC/ICP-IDMS for trimethyllead determinations in biological and environmental samples

An accurate and sensitive species-specific isotope dilution GC/ICPMS method was developed for the determination of trimethyllead (Me3Pb+) in biological and environmental samples. A trimethyllead spike was synthesized from 206Pb-enriched metallic lead by reaction of lead halide with methyllithium and subsequent formation of trimethyllead iodide. The isotopic composition of the spike solution was determined by GC/ICPMS after derivatization with tetraethylborate, and its concentration was determined by reverse isotope dilution analysis. The species-specific GC/ICP-IDMS method was validated by reference material CRM 605 (urban dust) certified for Me3Pb+. The method was also applied to determine the Me3Pb+ content in six biological reference materials (DORM 2, CRM 278, CRM 422, CRM 463, CRM 477, MURST-ISS-A2) and one sediment reference material (CRM 580) for which no certified values of this species exist. The Me3Pb+ concentrations in the biological reference materials vary in the range of 0.3-17 ng g(-1) (as Pb) except for the Antarctic Krill (MURST-ISS-A2), where the concentration was less than the detection limit of 0.09 ng g(-1), which was also found for the sediment. Up to 20% of total lead was methylated in the biological reference materials, whereas much higher methylation fractions were found for mercury. The method was also applied to seafood samples purchased from a supermarket with Me3Pb+ concentrations in the limited range of 0.3-0.7 ng g(-1). On the contrary, the portion of methylated lead in these samples varied over more than 2 orders of magnitude from 0.02 to 7.5%.     

Application of isotopically labeled methylmercury for isotope dilution analysis of biological samples using gas chromatography/ICPMS

An isotope dilution (ID) procedure for the determination of methylmercury (MMHg) in biological samples using an inductively coupled plasma mass spectrometer as detector after the capillary gas chromatographic separation (CGC/ICPMS) has been developed. For the first time, open-focused-microwave pretreatment has been used in conjunction with ID. Optimum conditions for the measurement of isotope ratios on the fast transient chromatographic peaks have been established. Mass bias was found to be about 1.5%/mass unit and was corrected by using the simultaneously measured thallium signals at 203Tl and 205Tl. After mass-bias correction, deviation of the theoretical mercury ratio values was found to be as low as 0.2%. Isotope ratio precisions based on the peak areas measurements were 0.3% RSD for 20 pg injected (as Hg absolute). The absolute detection limits were in the range of 20-30 fg for 202Hg and 201Hg. Methylmercury enriched in 201Hg has been synthesized by direct reaction with methylcobalamine. The concentration of the MMHg spike has been measured by reverse isotope dilution with a natural MMHg standard. The capabilities of CGC/ICPMS to measure isotope ratios were used to optimize sample derivatization by aqueous ethylation with NaBEt4 with respect to MMHg degradation pathways and quantitative recovery. The accuracy of the method developed has been validated with biological certified reference materials (CRM-463, DORM-1).     

Advantages of molecularly imprinted polymers LC-ESI-MS/MS for the selective extraction and quantification of chloramphenicol in milk-based matrixes. comparison with a classical sample preparation

A simple and fast selective extraction of the antibiotic chloramphenicol (CAP) from milk (raw milk, skimmed milk, and milk powder) using a molecularly imprinted polymer (MIP) sorbent is described. The method entails a single centrifugation step prior to loading the supernatant onto the MIP cartridge and subsequent elution with a mixture of solvents. CAP was further analyzed by isotope dilution liquid chromatography electrospray ionization tandem mass spectrometry (LC-ESI-MS/MS) operating in negative ionization acquisition mode. The advantages of the MIP approach were assessed by comparing the data generated from a classical solid-phase and liquid-liquid extractions procedure, previously developed in our laboratory. A better recovery of CAP due to an enhanced selectivity and a faster turnaround time (18 samples processed within 3 h compared to 8 h with the classical approach) were evidenced when using the MIP cleanup. The analysis of CAP in raw milk was further validated according to the 2002/657/EC European Union criteria for the analysis of veterinary drug residues at the minimum required performance limit (MRPL) of 0.3 microg/kg, using CAP-d(5) as internal standard. Non-internal-standard corrected recovery values ranged between 50% and 87% over the range of concentrations considered. The decision limit (CCalpha) and detection capability (CCbeta) were calculated to be 0.06 and 0.10 microg/kg, respectively.     

Determination of selenium by inductively coupled plasma mass spectrometry utilizing a new hydride generation sample introduction system.

An inductively coupled plasma mass spectrometer with a newly designed continuous flow hydride generator was used for the determination of Se in biological materials. The design of the hydride generator was important in minimizing interference from HCl and in maximizing analytical sensitivity. Two sample preparation procedures incorporating either 3.8 or 7.2 M HCl in the final sample solutions were compared. Interference from Cu was eliminated by the addition of 0.2 M NaI to the sodium borohydride solution (3.8 M method) or by maintaining a high concentration of HCl in the sample solution (7.2 M method). The 3.8 M method had the advantage of minimizing exposure of expensive equipment to corrosive HCl fumes, whereas the 7.2 M method did not contaminate equipment with I and had no measurable sample-to-sample cross-contamination. In practice, cross-contamination from sample to sample in both methods was negligible during analysis. An important factor in minimizing cross-contamination from sample to sample was the elimination of the air bubble normally entrained between samples. Determination of isotopic tracer enrichment was linear from 0 to 320% enrichment, which provided a broad range for isotope dilution analysis. A detection limit of 6.4 pg of Se was observed under optimum conditions, whereas a detection limit of 1.3 ng of Se was found for routine analysis of 1-g samples of plant material. Selenium was accurately determined by isotope dilution analysis in a variety of biological reference materials.     

罐装婴幼儿奶粉营养标签及营养素的调查分析

目的分析罐装信息,为消费者选购国内外婴幼儿奶粉提供细致参考。方法通过网络调查和实体店走访的形式,调查分析不同品牌、不同年龄阶段罐装奶粉的营养标签等信息。结果京东麦乐购母婴商城和实体店31种品牌罐装奶粉的营养标签标识率均为100%,其中标识率较高的营养成分包括能量、蛋白质、碳水化合物、脂肪、维生素(A,D,E,K,C)和矿物质(钙、铁、磷、锌)。美系罐装奶粉蛋白质含量标识数高于其他系别,但其他营养素标识数则没有显著差异。同一罐装奶粉品牌不同系列的营养标识中重要营养素含量大同小异,而不同品牌的罐装奶粉营养素含量标识数则差异较大。其中,美赞臣罐装奶粉注重提高婴幼儿脑部智力发育,其DHA和ARA含量标识数较高(P0.05);雅培罐装奶粉注重增强婴幼儿体质,其钙、铁、磷等矿物质含量的标识数较高(P0.05);惠氏罐装奶粉的叶黄素含量的标识数较高(P0.05),且含有天然胡萝卜素的标识。结论消费者按照婴幼儿的体质、生长阶段和生活喜好的不同,可根据营养标签来选择最合适的罐装奶粉。     

Determination of tin in human blood serum by radiochemical neutron activation analysis

A method was developed for the determination of tin in human serum by radiochemical neutron activation analysis, using the long-lived radioisotope Sn(T1/2 = 115.09 days). This radioisotope decays to a daughter isotope 113mIn, the most suitable nuclide for counting (T1/2 = 1.658 h, gamma-ray of 391.7 keV). Experience showed that, with the exception of the serum samples with the lowest tin levels, in the experimental conditions of the present study tin could mostly also be determined by using its radioisotope 117mSn(T1/2 = 13.61 days, gamma-ray of 158.5 keV). Samples were collected and prepared by using the procedure elaborated by the authors, which proved its effectiveness in preventing significant sample contamination on several occasions. Because samples had to be irradiated at 10(14) n.cm-2.s-1, dry ashing was necessary. After irradiation, tin was separated by solvent extraction of tin(IV) iodide from a sulfuric acid-ammonium iodide solution with toluene. The dry ashing and solvent extraction steps were exhaustively tested by means of radioactive tracer experiments whereas the accuracy and precision of the analytical method were thoroughly checked by analyzing biological reference materials (Bowen's kale powder, the NBS' bovine liver, the NBS' nonfat milk powder, and the "second-generation" biological reference material--freeze-dried human serum--for trace element determinations, developed by the authors).(ABSTRACT TRUNCATED AT 250 WORDS)     

Determination of chromium in urine by stable isotope dilution gas chromatography/mass spectrometry using lithium bis(trifluoroethyl)dithiocarbamate as a chelating agent

An isotope dilution gas chromatography/mass spectrometry method using lithium bis(trifluoroethyl)dithiocarbamate as a chelating agent is described for the determination of chromium in urine. A wet digestion procedure with HNO3-H2O2 is used for oxidizing the organic matter associated with urine samples. The isotope ratios are measured by selected ion monitoring in a general-purpose mass spectrometer using a 10-m fused silica capillary column. Memory effect, in sequential analyses of samples with different isotope ratios, was evaluated by preparing a series of synthetic mixtures and was found to be negligible. The accuracy of the method was verified by quantitation of chromium in the NIST freeze-dried urine reference material, SRM-2670, with a recommended chromium concentration of 13 micrograms/L in the normal level and certified chromium concentration of 85 +/- 6 micrograms/L in the elevated level.     

Analysis of hydrazine in drinking water by isotope dilution gas chromatography/tandem mass spectrometry with derivatization and liquid-liquid extraction

A new isotope dilution gas chromatography/chemical ionization/tandem mass spectrometric method was developed for the analysis of carcinogenic hydrazine in drinking water. The sample preparation was performed by using the optimized derivatization and multiple liquid-liquid extraction techniques. Using the direct aqueous-phase derivatization with acetone, hydrazine and isotopically labeled hydrazine-(15)N2 used as the surrogate standard formed acetone azine and acetone azine-(15)N2, respectively. These derivatives were then extracted with dichloromethane. Prior to analysis using methanol as the chemical ionization reagent gas, the extract was dried with anhydrous sodium sulfate, concentrated through evaporation, and then fortified with isotopically labeled N-nitrosodimethylamine-d6 used as the internal standard to quantify the extracted acetone azine-(15)N2. The extracted acetone azine was quantified against the extracted acetone azine-(15)N2. The isotope dilution standard calibration curve resulted in a linear regression correlation coefficient (R) of 0.999. The obtained method detection limit was 0.70 ng/L for hydrazine in reagent water samples, fortified at a concentration of 1.0 ng/L. For reagent water samples fortified at a concentration of 20.0 ng/L, the mean recoveries were 102% with a relative standard deviation of 13.7% for hydrazine and 106% with a relative standard deviation of 12.5% for hydrazine-(15)N2. Hydrazine at 0.5-2.6 ng/L was detected in 7 out of 13 chloraminated drinking water samples but was not detected in the rest of the chloraminated drinking water samples and the studied chlorinated drinking water sample.     

Determination of total sulfur at microgram per gram levels in geological materials by oxidation of sulfur into sulfate with in situ generation of bromine using isotope dilution high-resolution ICPMS

We have developed a new, simple, and accurate method for the determination of total sulfur at microgram per gram levels in milligram-sized silicate materials with isotope dilution high-resolution inductively coupled plasma mass spectrometry equipped with a flow injection system. In this method, sulfur can be quantitatively oxidized by bromine into sulfate with achievement of isotope equilibrium between the sample and spike. Detection limits for 32S+ and 34S+ in the ideal solution and silicate samples were 1 and 6 ng mL(-1) and 0.07 and 0.3 microg g(-1), respectively. The total blank was 46 ng, so that a 40-mg silicate sample containing 10 mirog g(-1) sulfur can be measured with a blank correction of < 10%. This total blank can be lowered to 8 ng if a low-blank air system is used for evaporations. To evaluate the applicability of this method, we analyzed not only silicate reference materials with sulfur content of 5.25-489 microg g(-1) and sample sizes of 13-40 mg but also the Allende meteorite with a sulfur content of 2%. The reproducibility for various rock types was < 9%, even though blank corrections in some samples of low sulfur content were up to 24%. This method is suitable for analyzing geological samples as well environmental samples such as soils, sediments, and water samples.     

Preparation of a Pu standard source: I. Isotope dilution alpha-ray spectrometry used for standardization

A ²³⁸Pu source was prepared by electrodeposition method. For the standardization of the source, isotope dilution alpha-ray spectrometry (IDAS) was investigated: The content of ²³⁸Pu in a sample solution was determined both by IDAS and by isotope dilution mass spectrometry (IDMS) using a standard reference material of ²³⁹Pu as a spike. The estimated uncertainty in the determination of ²³⁸Pu is 0.13% for IDAS, and the factor of IDAS/IDMS is calculated to be 1.0000±0.0015.